CN104224409A - Artificial cotyla cup, magnetron sputter coating device and preparation method of artificial cotyla cup and magnetron sputter coating device - Google Patents

Abstract

The invention discloses an artificial cotyla cup, a magnetron sputter coating device and a preparation method of the artificial cotyla cup and the magnetron sputter coating device. Based on low temperature magnetron sputter coating equipment, existing equipment is further transformed and upgraded, and a new material system and a preparation method thereof are built on a high molecular polyethylene cotyla cup based on the material system, and the problem that the binding force between a membrane and a matrix is bad is solved; meanwhile, the problems that high molecular polyethylene is easily oxidized and carbonized can be solved through a low temperature magnetron sputtering technology. On such basis, a nano multi-layer structure GLC (Gas Liquid Chromatography) membrane alternately plated and covered with a graphite-like membrane and a diamond-like membrane is built by using the super lubricity of the graphite-like membrane and the superhardness of the diamond-like membrane. Therefore, the wear resistance of the high molecular polyethylene cotyla cup can be improved, the precision deviation of a joint caused by creep deformation can be restrained, and a novel artificial hip joint cotyla cup with the super wear-resistant nano multi-layer structure GLC membrane with the functions of high hardness, frictional wear resistance and self-lubrication can be built.

Description

An artificial joint acetabular cup, a magnetron sputtering coating device and a preparation method thereof

technical field

The invention relates to the field of materials and medical devices, in particular to an artificial acetabular cup product coated with a nanometer multilayer structure carbon film, a magnetron sputtering coating device for producing an artificial acetabular cup and a preparation method thereof.

Background technique

High molecular polyethylene has relatively superior physical, chemical, and mechanical properties, and is still the mainstream material for artificial joint cups. However, many years of clinical observation and experimental research have shown that the high molecular polyethylene acetabular cup is compatible with the metal femoral head, the relative hardness is low, and it bears a large load for a long time. Loosening leads to a shortened service life of the artificial hip joint and increases the clinical risk of the patient's second or third artificial hip revision surgery.

In recent years, artificial hip joint prosthesis has tried the compatibility of "pottery-pottery" and "gold-gold" with the same material, hoping to solve the interface wear problem of different materials. However, clinical application has proved that "Tao-Tao" and "Gold-Gold" also have insurmountable defects, such as "Tao-Tao" joints are fragile, which limits the amount of activity and range of activities of the postoperative population; "Gold-Gold" "Joints have stricter requirements on surgical conditions and doctors' surgical skills. A slight deviation in joint replacement will increase the wear of the joint edges, resulting in a large amount of debris and abnormal noise. Therefore, the mainstream products of artificial hip joints still choose to upgrade the technology in the way of high molecular polyethylene acetabular cup-metal ball head compatibility.

The wear of high molecular polyethylene is mainly affected by material properties and processing methods. Therefore, scholars at home and abroad have improved the wear resistance of high molecular polyethylene through cross-linking modification and physical modification. However, radiation cross-linking modification has the problem of oxidation and catalysis of high molecular weight polyethylene during the cross-linking process; ion implantation cross-linking modification, ion implantation layer depth is limited (when the implantation energy is 50-100keV, the layer thickness is about 0.1-0.2μm), It cannot meet the requirements of medical polymer polyethylene materials. Although the physical filling method improves the wear resistance, it reduces important mechanical properties such as tensile strength, impact strength and elongation at break, and is currently mainly used in the industrial field.

Coating technology can add additional properties to the base material. Scholars at home and abroad have attempted to coat the surface of the polymer polyethylene acetabular cup with a diamond-like film to increase its wear resistance on the basis of ensuring the material properties of the polymer polyethylene. However, as a soft material, high molecular polyethylene has poor heat resistance, is easy to carbonize and oxidize, and deposits a coating on it, which requires high coating technology and equipment. How to realize high molecular polyethylene surface coating under non-destructive conditions , The design of the coating material system, the standard of the process and the performance of the equipment are extremely demanding. At present, there is no similar product on the market in the world.

The applicant's previous patent, publication number: 201210151152.2, discloses a magnetron sputtering coating device, a nano-multilayer film and its preparation method. By using a special sputtering device and sputtering technology, the polymer polyethylene The nano-multilayer structure carbon film technology is applied to the artificial joints of the substrate, and the transition layer of titanium carbide and graphite-like, the multi-layer structure of graphite-like layer and diamond-like layer alternately stacked, and the diamond-like top layer film structure are coated respectively. The technical solution starts from the material system, and according to the material characteristics of high molecular polyethylene, such as poor heat resistance, easy oxidation, easy carbonization, easy dissociation of the main chain or side chain, and easy cross-linking, a new high-molecular polyethylene acetabular cup surface is constructed. The material system and its preparation method solve the problem of poor bonding between the film and the substrate. At the same time, the low-temperature magnetron sputtering technology solves the problem of easy oxidation and carbonization of high molecular polyethylene.

Through research and practice, the applicant improved the deficiencies of the technical solution applied for, and at the same time proposed an improvement plan for the device and method of producing the product, so as to meet the requirements of the improved technical solution.

Contents of the invention

The purpose of the present invention is to at least solve one of the above-mentioned technical defects and improve the service life of the artificial joint prosthesis.

Embodiments of the present invention are achieved through the following technical solutions:

An artificial joint acetabular cup, comprising a substrate and a nano-multilayer film plated on the substrate; the nano-multilayer film includes a pure Ti bottom layer cross-linked with the substrate, a Ti and TiC transition layer on the pure Ti bottom layer , the composite layer on the Ti and TiC transition layer and the pure carbon film layer on the composite layer; the composite layer is a nano-multilayer structure composed of graphite-like and diamond-like monolayer films alternately deposited; from the bottom layer to the composite layer direction Above, the mass percentage of Ti in the Ti and TiC transition layers decreases gradually, and the mass percentage of C gradually increases.

Further, the base body is a high molecular polyethylene acetabular cup.

Further, the bonding force between the substrate and the nano-multilayer film is >60N.

Further, the hardness of the nano-multilayer film is >20Gpa.

Further, the thickness of the pure Ti bottom layer is 100-300 nm.

Further, the thickness of the Ti and TiC transition layer is 300-500 nm.

Further, in the nano-multilayer structure composed of graphite-like and diamond-like single-layer films alternately deposited in the composite layer, the thickness of the single-layer film is 10-25nm, and the total thickness of the composite layer is 1.5-5.0um.

Further, the thickness of the pure carbon film is 100nm-200nm.

The embodiment of the present invention also provides a device for producing the above-mentioned artificial joint acetabular cup, which is used to coat the nano-multilayer film on the substrate; it includes a vacuum coating chamber, a sputtering target, and a turret platform on the base of the vacuum coating chamber and the workpiece rack on the turntable, and the first rotating system that drives the turntable to rotate around the central axis of the turntable; the sputtering target is arranged around the turntable and is perpendicular to the turntable, and the sputtering target includes two second A sputtering target and a second sputtering target, the sputtering target is located on a circle concentric with the turret, the arc between the two first sputtering targets is 180-240 degrees, the second The sputtering target is equally divided into the arc; the turret is fixedly provided with a partition that passes through the surface of the turret, and in the direction perpendicular to the turret, both ends of the partition exceed the sputtering target. two ends; the bottom of the first sputtering target is provided with a magnetic field shielding layer.

Further, the first sputtering target is a graphite target, and the second sputtering target is a titanium target or a tantalum target.

Further, the magnetic field shielding layer is a silicon steel gasket.

Further, the baffle passes through the turret along the diameter of the turret, and the width of the baffle is larger than the diameter of the turret.

Further, the distance between the separator and the circumference of the sputtering target is 2-10 cm.

Further, the sputtering target is rectangular.

Further, the material of the separator is titanium, aluminum, stainless steel or a combination thereof.

Further, it also includes: a second rotating system that drives the turret table to rotate around the central axis of the workpiece holder.

Further, the workpiece rack is arranged on the turret platform through a support rod, and a plurality of workpiece racks are arranged at intervals on the same support rod.

Further, the sputtering target is arranged on the inner wall of the vacuum coating chamber.

Further, the arc between the two first sputtering targets is 180 degrees, and the sputtering target also includes another second sputtering target, the two second sputtering targets are arranged opposite to each other, and the other first sputtering target The second sputtering target is idle.

The embodiment of the present invention also provides a method for producing an artificial joint acetabular cup using the above-mentioned production device of the artificial joint acetabular cup, which is used to coat a nanometer multi-layer film on the substrate to keep the turret rotating at a constant speed, including:

Step 1) Adjust the initial magnetic field strength G1 with the magnetic field shielding layer, so that it meets the requirements of non-destructive sputtering on the surface of the high molecular polyethylene acetabular cup;

Step 2) Control the initial working pressure of the coating chamber to be P1, and inject 99.9% argon gas to clean the target and substrate;

Step 3) Control the working pressure P2 of the coating chamber, and control the working magnetic field strength of the first sputtering target to G2; the second sputtering target uses the initial I1 current and bias voltage V1 to coat the bottom layer of the pure titanium layer on the substrate for the first predetermined time. the sputtering;

Step 4) Keep the bias voltage of the second sputtering target constant, and start from the initial current I1, every first interval time T1, the operating current of the second sputtering target is reduced by ΔI1 until its operating current is the first Predetermined current value; at the same time, the first sputtering target starts from the initial operating current I2, the bias value is V2, and every second interval T2, the operating current of the first sputtering target increases by ΔI2 until its operating current is A second predetermined current value; the operating voltages of the first sputtering target and the second sputtering target remain unchanged, and sputtering is performed for a second predetermined duration;

Step 5) Keep the operating current of the second sputtering target at the first predetermined current value or set and maintain it at the third predetermined current value, maintain the operating current of the first sputtering target at the second predetermined current value or set the first The operating current of the sputtering target is set and maintained at a fourth predetermined current value, the operating voltages of the first sputtering target and the second sputtering target remain unchanged, and sputtering is performed for a third predetermined time;

Step 6) Set the operating current of the second sputtering target to zero, and keep the operating current of the first sputtering target at the operating current of step 3) or set and maintain the operating current of the first sputtering target at the first Five preset current values, performing sputtering for a fourth preset duration.

Optionally, the initial magnetic field strength G1 is 20-30GT; the initial working pressure P1 is 1.0mPa; the working pressure P2 is controlled at 130mPa-250mPa; the working magnetic field strength G2 is 10-150mT; the second sputtering The initial I1 current for the target is 3.0-5.0A, the bias voltage V1 is 90-150V, the ΔI1 is 0.5-1.0A, the first predetermined current value is 0.5-1.0A, and the initial operating current I2 is 0, The ΔI2 is 0.5-1.0A, the second predetermined current value is 3.0-6.0A, the bias voltage V2 is 60-100V; both T1 and T2 are positive numbers greater than .

Further, the first predetermined duration is 10-30 minutes.

Further, the second predetermined duration is 10-30 minutes.

Further, the third predetermined duration is 5-10 hours.

Further, the fourth predetermined duration is 10-20 minutes.

Further, the first interval T1 is 3-10 minutes; the second interval T2 is 3-10 minutes.

Further, the temperature of the whole coating process is controlled at 30-40°C.

The embodiment of the present invention further transforms and upgrades the existing equipment on the basis of the low-temperature magnetron sputtering coating equipment, and starts from the material system. Based on the characteristics of the material that the chain is easy to dissociate and cross-link, a new material system and its preparation method are constructed on the surface of the high molecular polyethylene acetabular cup. Using Ti as the substrate, cross-linked with high-molecular polyethylene, and using the gradient change in the ratio of Ti and C elements as the transition layer, it solves the problem of poor bonding between the film and the substrate. At the same time, the low-temperature magnetron sputtering technology solves the problem of high Molecular polyethylene is easy to oxidize and carbonize.

On this basis, using the superlubricity of the graphite-like structure film and the superhardness of the diamond-like structure film structure, a nano-multilayer structure GLC (graphite-like-carbon) with graphite-like film and diamond-like film alternately plated is constructed. membrane.

The embodiment of the present invention improves the wear resistance of the high molecular polyethylene acetabular cup, curbs the deviation of joint precision caused by creep, and constructs a super wear-resistant nano-multilayer structure GLC film with high surface hardness, strong bonding force and self-lubricating function A new type of artificial hip joint cup.

Description of drawings

FIG. 1 is a schematic diagram of a three-dimensional structure of a magnetron sputtering coating device according to an embodiment of the present invention;

Fig. 2 is a top view schematic diagram of the magnetron sputtering coating device shown in Fig. 1;

Fig. 3 is that Ti bottom layer and nanometer multi-layer structure carbon film are plated with polyethylene;

Figure 4 is the Raman spectrum of the coated nanometer multilayer structure carbon film polymer polyethylene.

Detailed ways

Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary only for explaining the present invention and should not be construed as limiting the present invention.

An artificial joint acetabular cup in an embodiment of the present invention includes a substrate and a nano-multilayer film coated on the substrate; in an embodiment of the present invention, the substrate is a device that can be implanted into the human body, such as a bone joint head or an acetabular cup etc., can also be other substrates, such as engineering props, etc. The material of the substrate can be metal or alloy material or other materials, etc. The substrate in this embodiment is a high molecular polyethylene acetabular cup.

The nano multilayer film includes a pure Ti bottom layer cross-linked with the substrate, a Ti and TiC transition layer on the pure Ti bottom layer, a composite layer on the Ti and TiC transition layer, and a pure carbon film layer on the composite layer; The composite layer is a nano-multilayer structure composed of graphite-like and diamond-like monolayers alternately deposited; from the bottom layer to the direction of the composite layer, the mass percentage of Ti in the Ti and TiC transition layer gradually decreases, and the mass percentage of C As the percentage increases gradually, it has a better bonding force with the bottom layer, and reduces the penetration of titanium from the bottom layer to the transition layer. At the same time, it has low internal stress and good lubricity, and improves the lubricity through the pure carbon film layer on the top layer. The bonding force between the substrate and the nano-multilayer film is >60N, and the hardness of the nano-multilayer film is >20Gpa.

As shown in Fig. 3 and Fig. 4, Fig. 3 is a Ti bottom layer and a nano-multilayer structure carbon film coated with high molecular polyethylene; it can be observed from Fig. 3 that after the Ti bottom layer is plated, the surface of the high molecular polyethylene presents a metallic luster, There is no carbonization phenomenon; the carbon film with nanometer multilayer structure is plated, and the surface of high molecular polyethylene is bright black. Fig. 4 is ^the Raman spectrum of coated nano-multilayer structure carbon film polymer polyethylene; through the Raman spectrum analysis of Fig ^. Characteristic peaks of graphite-like (sp2) and diamond-like (sp3).

It should be noted that, in the embodiment of the present invention, the transition layer of Ti and TiC means that the transition layer is a layer mixed with titanium and titanium carbide, that is to say, the transition layer is mixed with titanium and titanium carbide.

In the embodiment of the present invention, there is no limitation on the number of layers of the nano-multilayer structure composed of graphite-like and diamond-like monolayer films alternately deposited in the composite layer.

As shown in Fig. 1 and Fig. 2, the embodiment of the present invention also discloses a kind of device of producing artificial joint acetabular cup, is used for plating nanometer multi-layer film on substrate; The production of artificial joint acetabular cup in the present embodiment The device is a magnetron sputtering coating device, including a vacuum coating chamber, a sputtering target, a turret on the base of the vacuum coating chamber, a workpiece frame on the turret, and a first rotation that drives the turret to rotate around the central axis of the turret. system, temperature control system; at the same time, the device also includes other necessary components, such as a heating device, a cooling water circulation system, and a power supply system electrically connected to the sputtering target (not shown in the figure). The sputtering target is arranged around the turret and is perpendicular to the turret, the sputtering target includes two first sputtering targets and a second sputtering target, and these sputtering targets are located on a circle concentric with the turret, The circumference of the location of the sputtering target can be an actual component, such as the inner wall of the vacuum coating chamber 100, or a virtual circumference such as any position between the turntable and the vacuum coating chamber, wherein the two first sputtering targets 120a , 120b are arranged relatively parallel, and divide the circumference 104 equally, and the second sputtering target 130 equally divides the arc between the two first sputtering targets 120a, 120b, that is, the two first sputtering targets The arc between the targets 120a, 120b is basically 180°, the arc between the second sputtering target 130 and the first sputtering target 120a, 120b is basically 90°, and the first sputtering target 120a, 120b can be a certain A sputtering target of one element, the second sputtering target can be a sputtering target of another element, and the material of the sputtering target can be selected according to the specific product that needs to be sputtered. For example, in this embodiment, the The first sputtering target is a graphite target, and the second sputtering target is a titanium target. In other embodiments, the first sputtering target can be a carbon target, and the second sputtering target can also be a tantalum target. target etc.

In other embodiments, the two first sputtering targets and one second sputtering target can also be arranged at intervals of other angles on the circumference, for example, the circle between the two first sputtering targets 120a, 120b The radian of the arc is other angles between 180°-240°, and a second sputtering target bisects the arc, so that the arc of the arc between the second sputtering target and the first sputtering target can be Between 90° and 120°, the arc of the arc between the second sputtering target 130 and the first sputtering target 120a, 120b is 120°.

In this embodiment, the turret platform 102 is a round platform, and a partition 110 is fixedly arranged on the turret platform 102. Preferably, the partition 110 is a straight plate, and the material of the partition can be titanium, aluminum, stainless steel etc. or a combination of these materials, the partition 110 is vertically arranged on the turret 102 through the diameter of the turret, and the turret 102 is divided into two mutually independent regions 102-1, 102-2 by the partition 110 , in the direction perpendicular to the turret platform, both ends of the partition 110 exceed the two ends of the sputtering targets 120a, 120b, 130, so that the partition blocks the sputtering target on the other side of a certain area, which can make the area Only accept the coating of the sputtering target facing this area. More preferably, in order to achieve a better blocking effect, the width of the partition is greater than the diameter of the turntable platform, wherein the width refers to that the partition passes through the turntable. The length in the diameter direction of the platform, more preferably, the distance d between the partition and the circumference of the sputtering target is 2-10 cm.

The turret 102 is provided with a first rotation system (not shown) that drives the turret to rotate around its central axis, that is, the turret and partitions rotate around the central axis of the turret together with the turret. In the above-mentioned position of the three sputtering targets, when the turret platform is rotated to any position, under the shield of the partition plate 102, a region 102-1 of the turret platform faces the first sputtering target 120a (such as graphite target) and the second sputtering target 130 (titanium target), so that the product (or substrate) to be coated in this region 102-1 can be coated with titanium or diamond-like carbon: titanium carbide film (a mixed film layer of titanium and titanium carbide ), and another area 102-2 of the turret platform faces the first sputtering target 120b (graphite target), so that the product in this area 102-2 is coated with a carbon film, and as the turret platform rotates, different areas The products on the screen will be layered with titanium or diamond-like stone: titanium carbide film and carbon film, so as to realize the coating of nano-multilayer film on the product, and by adjusting the speed of the turntable, the single-layer film can be controlled. Thickness, the structure of the device is simple, the control of the process is simple, the preparation of the multi-layer film is solved, and it is suitable for industrialization.

In other embodiments, the partition 110 can also be vertically arranged at other positions of the turret, and can also be a bent plate or any other partition that can divide the turret into two mutually independent regions.

In this embodiment, the device also has a second rotating system that drives the turret to rotate around the central axis of the workpiece rack, that is to say, the workpiece rack can rotate by itself, and a plurality of Workpiece rack 140, a plurality of workpiece racks 150 can be arranged at intervals on the same support rod 160 to improve processing efficiency. on the circumference. Through the rotation of the workpiece rack, the film layer coated on the product to be coated on each workpiece rack can have better uniformity.

The above is the magnetron sputtering coating device of the preferred embodiment of the present invention. The difference from this embodiment is that in another preferred embodiment, there are four sputtering targets (not shown in the figure), and Around the turntable, that is to say, the sputtering target includes two first sputtering targets and two second sputtering targets, the two first sputtering targets are opposite to each other, and the two second sputtering targets are opposite to each other. setting, four sputtering targets equally divide the circumference, but when preparing multilayer films, one of the second sputtering targets does not work, that is, two first sputtering targets and one second sputtering target The corresponding target current, voltage and other parameters are set to perform target sputtering coating, while the other second sputtering target does not perform target sputtering coating, and is in an idle state. In this embodiment, although four sputtering targets are provided, one of the sputtering targets is not sputtered.

In all embodiments of the present invention, a magnetic field shielding layer is provided on the bottom of the first sputtering target. In this embodiment, using the magnetic field shielding effect of silicon steel, two 5mm thick silicon steel sheets and three layers of heat conduction film are added to the bottom of the first sputtering target (graphite target); two pure graphite targets are perpendicular to a pure Ti target Alternately arranged at an angle of 120 degrees in the horizontal plane. According to the occurrence conditions of surface oxidation and carbonization of high molecular polyethylene and other polymers, adjust the strength of the magnetic field to meet the requirements of non-destructive sputtering on the surface of high molecular polyethylene and other polymers.

The magnetron sputtering coating device according to the embodiment of the present invention has been described in detail above. During the preparation, various process parameters are set according to specific requirements to prepare the nano-multilayer film. For this reason, an embodiment of the present invention also provides a method for coating a substrate using any of the above-mentioned magnetron sputtering coating devices, the method comprising:

Step 1) Adjust the initial magnetic field strength G1 with the magnetic field shielding layer, so that it meets the requirements of non-destructive sputtering on the surface of the high molecular polyethylene acetabular cup;

Step 2) Control the initial working pressure of the coating chamber to be P1, and inject 99.9% argon gas to clean the target and substrate;

Step 3) Control the working pressure P2 of the coating chamber, and control the working magnetic field strength of the first sputtering target to G2; the second sputtering target uses the initial current I1 and bias voltage V1 to coat the bottom layer of the pure titanium layer on the substrate, and perform the first predetermined time the sputtering;

Step 4) Keep the bias voltage of the second sputtering target constant, and start from the initial current I1, every first interval time T1, the operating current of the second sputtering target is reduced by ΔI1 until its operating current is the first Predetermined current value; at the same time, the first sputtering target starts from the initial operating current I2, the bias value is V2, and every second interval T2, the operating current of the first sputtering target increases by ΔI2 until its operating current is A second predetermined current value; the operating voltages of the first sputtering target and the second sputtering target remain unchanged, and sputtering is performed for a second predetermined duration;

Step 5) Keep the operating current of the second sputtering target at the first predetermined current value or set and maintain it at the third predetermined current value, maintain the operating current of the first sputtering target at the second predetermined current value or set the first The operating current of the sputtering target is set and maintained at a fourth predetermined current value, the operating voltages of the first sputtering target and the second sputtering target remain unchanged, and sputtering is performed for a third predetermined time;

Step 6) Set the operating current of the second sputtering target to zero, and keep the operating current of the first sputtering target at the operating current of step 3) or set and maintain the operating current of the first sputtering target at the first Five preset current values, performing sputtering for a fourth preset duration.

In the embodiment of the preparation method of the present invention, all three sputtering targets work, that is, two first sputtering targets and one second sputtering target work, and also include the implementation of another second sputtering target In the example, the second sputtering target is in an idle state, and sputtering has not been performed during the preparation of the nanometer multilayer film.

In some embodiments, the first sputtering target of the magnetron sputtering coating device is a graphite target, and the second sputtering target is a titanium target. First, the substrate to be coated (or the product to be coated) is placed in the vacuum coating chamber. On the workpiece rack, use 99% alcohol to ultrasonically clean the polymer polyethylene cup for 5 minutes, then use ultrapure water to ultrasonically clean for 5 minutes, and dry it with cold air.

At the same time, use a silicon steel gasket to adjust the initial magnetic field strength to 20-30GT to meet the requirements of non-destructive sputtering on the surface of the polymer polyethylene acetabular cup; when the vacuum coating chamber is evacuated to 1.0mPa, 99.9% argon gas is introduced to clean it Target and substrate 5min.

Then, sputtering is performed. During the whole sputtering process, the turret rotates at a constant speed, and the substrate to be coated can also rotate by itself.

Specifically, the working pressure of the coating chamber is controlled to be maintained at 130mPa-250mPa, the magnetic field strength of the first sputtering target (such as graphite target) is 10-150mT, the current of the second sputtering target (such as titanium target) is 2.0-5.0A, and the bias voltage is 90 Coating the bottom layer of pure titanium layer on the substrate at -150V, the coating time is 10-30min, and the thickness is 100-300nm.

Then the current of the second sputtering target is changed with a gradient of 0.5-1.0A every time, and gradually drops from 3.0-5.0A to 0.5-1.0A after 5 times. At the same time, the two first sputtering targets (graphite targets) The current changes with a gradient of 0.5-1.0A per rise, and gradually rises from 0 to 3.0-6.0A after 6 times, that is to say, the current of the second sputtering target decreases stepwise, and the current of the first sputtering target The current increases stepwise, and their increasing and decreasing ranges can be the same or different, and the interval time can be the same or different. During the whole process, their target voltage remains constant and the bias voltage is 60-100V, Ti and TiC gradient films are plated, the plating time is 10-30min, and the thickness is 300-500nm.

Then keep the current and bias value of the second sputtering target and the two first sputtering targets unchanged, and plate a nano-multilayer structure carbon film composed of graphite-like and diamond-like single layers alternately deposited on the basis of the transition layer. The film thickness is 10-25nm, the total thickness is 1.5-5.0um, and the total time is 5-10h. The current of the second sputtering target is set to 0, and the pure carbon film is continuously deposited on the multi-layer film structure for 10-20 minutes, and the thickness of the pure carbon film is 100nm-200nm. Therefore, the total thickness of the nano-multilayer carbon film is 2.0-6.0 μm, and the temperature of the whole coating process is controlled at 30-40° C.

Example 1

The two first sputtering targets of the magnetron sputtering coating device are graphite targets, and the second sputtering target is a titanium target. The arc between the second sputtering target and the first sputtering target in the sputtering device is basically 90 degrees, the rotation speed of the turret is 1.5rpm, and the substrate to be coated rotates by itself. Before coating, first place the substrate to be coated (or the product to be coated) on the workpiece rack in the vacuum coating room, use 99% alcohol to ultrasonically clean the high molecular polyethylene cup for 5 minutes, and then use ultrapure water to ultrasonically clean it for 5 minutes , dry with cold air.

At the same time, the initial magnetic field strength of 20GT was adjusted with a silicon steel gasket to meet the requirements of non-destructive sputtering on the surface of the high molecular polyethylene acetabular cup; when the vacuum coating chamber was evacuated to 1.0mPa, 99.9% of argon gas was introduced to clean the target And substrate 5min.

Then, sputtering is performed. During the whole sputtering process, the turret rotates at a constant speed, and the substrate to be coated can also rotate by itself.

Specifically, the working pressure of the coating chamber is controlled to be maintained at 150mPa, the magnetic field strength of the first sputtering target (graphite target) is 80mT, the current of the second sputtering target (titanium target) is 3.0A, and the bias voltage is 90V to coat a pure titanium layer on the substrate For the bottom layer, the coating time is 10min, and the coating thickness is 150nm.

Then, the current of the second sputtering target was changed with a gradient of 0.5A every time, and gradually dropped from 3.0A to 0.5A after 5 times. At the same time, the current of the two first sputtering targets (graphite targets) was increased by 0.5 A is a gradient change, which gradually rises from 0 to 3.0A after 6 times, that is to say, the current of the second sputtering target decreases stepwise, and the current of the first sputtering target increases stepwise, and their increase The magnitudes of reduction and reduction can be the same or different, and the time intervals can be the same or different. During the whole process, their target voltage was kept constant and the bias voltage was 60V, Ti and TiC gradient films were plated, the plating time was 20min, and the plating thickness was 350nm (the proportion of C gradually increased, and the proportion of Ti gradually decreased).

Then keep the current and bias value of the second sputtering target and the two first sputtering targets unchanged, and plate a nano-multilayer structure carbon film composed of graphite-like and diamond-like single layers alternately deposited on the basis of the transition layer. The film thickness is 10-25nm, the total thickness is 2.4um, and the total time is 8h. The current of the second sputtering target is set to 0, and the pure carbon film is continuously deposited on the multilayer film structure for 10 min, and the thickness of the pure carbon film is 100 nm. As a result, the total thickness of the nano-multilayer carbon film is 3.0 μm, the temperature of the coating process is controlled from 27°C room temperature to 37°C working temperature, the bonding force of the film base is 87N, and the film hardness is 27.5Gpa.

Example 2

The two first sputtering targets of the magnetron sputtering coating device are graphite targets, and the second sputtering target is a titanium target. The arc between the second sputtering target and the first sputtering target in the sputtering device is basically 90 degrees, the rotation speed of the turret is 2.0rpm, and the substrate to be coated rotates. Before coating, first place the substrate to be coated (or the product to be coated) on the workpiece rack in the vacuum coating room, and use 99% alcohol to clean it ultrasonically After 5 minutes of polymer polyethylene cups, ultrasonically clean them with ultrapure water for 5 minutes, and dry them with cold air.

At the same time, the initial magnetic field strength of 25GT was adjusted with a silicon steel gasket to meet the requirements of non-destructive sputtering on the surface of the high molecular polyethylene acetabular cup; when the vacuum coating chamber was evacuated to 1.0mPa, 99.9% of argon gas was introduced to clean the target And substrate 5min.

Then, sputtering is performed. During the whole sputtering process, the turret rotates at a constant speed, and the substrate to be coated can also rotate by itself.

Specifically, the working pressure of the coating chamber is controlled to be maintained at 250mPa, the magnetic field strength of the first sputtering target (graphite target) is 150mT, the current of the second sputtering target (titanium target) is 2.0A, and the bias voltage is 100V to coat a pure titanium layer on the substrate For the bottom layer, the coating time is 15min, and the coating thickness is 250nm.

Then, the current of the second sputtering target was changed with a gradient of 0.5A every time, and gradually dropped from 3.5A to 1.0A after 5 times. A is a gradient change, which gradually rises from 0 to 3.0A after 6 times, that is to say, the current of the second sputtering target decreases stepwise, and the current of the first sputtering target increases stepwise, and their increase The magnitudes of reduction and reduction can be the same or different, and the time intervals can be the same or different. During the whole process, their target voltage was kept constant and the bias voltage was 80V, Ti and TiC gradient films were plated, the plating time was 25min, and the plating thickness was 450nm (the proportion of C gradually increased, and the proportion of Ti gradually decreased).

Then keep the current and bias value of the second sputtering target and the two first sputtering targets unchanged, and plate a nano-multilayer structure carbon film composed of graphite-like and diamond-like single layers alternately deposited on the basis of the transition layer. The film thickness is 10-25nm, the total thickness is 2.0um, and the total time is 6h. The current of the second sputtering target is set to 0, and the pure carbon film is continuously deposited on the multilayer film structure for 15 minutes, and the thickness of the pure carbon film is 150 nm. As a result, the total thickness of the nano-multilayer carbon film is 2.75 μm, the temperature of the whole coating process is controlled from room temperature of 27°C to the working temperature of 37°C, the bonding force of the film base is 90N, and the film hardness is 27.8Gpa.

Example 3

The two first sputtering targets of the magnetron sputtering coating device are graphite targets, and the second sputtering target is a titanium target. The arc between the second sputtering target and the first sputtering target in the sputtering device is basically 90 degrees, the rotation speed of the turret is 2.5rpm, and the substrate to be coated rotates on its own. Before coating, first place the substrate to be coated (or the product to be coated) on the workpiece rack in the vacuum coating room, and use 99% alcohol for ultrasonic cleaning After 5 minutes of polymer polyethylene cups, ultrasonically clean them with ultrapure water for 5 minutes, and dry them with cold air.

At the same time, use a silicon steel gasket to adjust the initial magnetic field strength to 30GT, so that it meets the requirements of non-destructive sputtering on the surface of the high molecular polyethylene acetabular cup; and when the vacuum coating chamber is evacuated to 1.0mPa, 99.9% argon gas is introduced to clean the target And substrate 5min.

Then, sputtering is performed. During the whole sputtering process, the turret rotates at a constant speed, and the substrate to be coated can also rotate by itself.

Specifically, the working pressure of the coating chamber is controlled to be maintained at 220mPa, the magnetic field strength of the graphite target is 110mT, the second sputtering target (titanium target) current is 3.0A, and the bias voltage is 150V to coat the bottom layer of the pure titanium layer on the substrate, and the coating time is 20min. The coating thickness is 300nm.

Then, the current of the second sputtering target was changed with a gradient of 0.8A every time, and gradually dropped from 5.0A to 1.0A after 5 times. At the same time, the current of the two first sputtering targets (graphite targets) was increased by 1.0A A is a gradient change, gradually rising from 0 to 6.0A after 6 times, that is to say, the current of the second sputtering target decreases stepwise, and the current of the first sputtering target increases stepwise, and their increase The magnitudes of reduction and reduction can be the same or different, and the time intervals can be the same or different. During the whole process, their target voltage was kept constant and the bias voltage was 100V. Ti and TiC gradient films were plated, the plating time was 30min, and the plating thickness was 500nm (the proportion of C gradually increased, and the proportion of Ti gradually decreased).

Then keep the current and bias value of the second sputtering target and the two first sputtering targets unchanged, and plate a nano-multilayer structure carbon film composed of graphite-like and diamond-like single layers alternately deposited on the basis of the transition layer. The film thickness is 10-25nm, the total thickness is 3.5um, and the total time is 10h. The current of the second sputtering target is set to 0, and the pure carbon film is continuously deposited on the multilayer film structure for 20 minutes, and the thickness of the pure carbon film is 200 nm. As a result, the total thickness of the nano-multilayer carbon film is 4.5 μm, the temperature of the whole coating process is controlled from room temperature of 27°C to the working temperature of 37°C, the bonding force of the film base is 95N, and the film hardness is 28.5Gpa.

Although the embodiments of the present invention have been shown and described, those skilled in the art can understand that various changes, modifications and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. and modifications, the scope of the invention is defined by the appended claims and their equivalents.

Claims (27)

1. An artificial joint acetabular cup comprises a substrate and a nano-multilayer film coated on the substrate; it is characterized in that: the nano-multilayer film includes a pure Ti bottom layer cross-linked with the substrate, on the pure Ti bottom layer The Ti and TiC transition layer, the composite layer on the Ti and TiC transition layer, and the pure carbon film layer on the composite layer; the composite layer is a nano-multilayer structure composed of graphite-like and diamond-like monolayer films alternately deposited; From the bottom layer to the composite layer, the mass percentage of Ti in the Ti and TiC transition layer gradually decreases, and the mass percentage of C gradually increases. 2. The artificial joint acetabular cup according to claim 1, characterized in that: the base body is a high molecular polyethylene acetabular cup. 3. The artificial joint acetabular cup according to claim 1, characterized in that: the bonding force between the matrix and the nano-multilayer film is >60N. 4. The artificial joint acetabular cup according to claim 1, 2 or 3, characterized in that: the hardness of the nano-multilayer film is >20Gpa. 5. The artificial joint acetabular cup according to claim 1, characterized in that: the thickness of the pure Ti bottom layer is 100-300nm. 6. The artificial joint acetabular cup according to claim 1, characterized in that: the thickness of the Ti and TiC transition layer is 300-500nm. 7. The artificial joint acetabular cup according to claim 1, characterized in that: in the nano-multilayer structure composed of graphite-like and diamond-like single-layer films of the composite layer alternately deposited, the thickness of the single-layer film is 10-25nm, The total thickness of the composite layer is 1.5-5.0um. 8. The artificial joint acetabular cup according to claim 1, characterized in that: the thickness of the pure carbon film is 100nm-200nm. 9. A device for producing the artificial joint acetabular cup according to any one of claims 1 to 8, characterized in that: it includes a vacuum coating chamber, a sputtering target, a turntable on the base of the vacuum coating chamber, and a turntable. The workpiece frame, and the first rotating system that drives the turret to rotate around the central axis of the turret; the sputtering target is arranged around the turret and is perpendicular to the turret, and the sputtering target includes two first sputtering targets And a second sputtering target, the sputtering target is located on the circumference concentric with the turret, the arc between the two first sputtering targets is 180-240 degrees, the second sputtering target etc. Divide the arc; the turret is fixedly provided with a partition that passes through the surface of the turret, and in a direction perpendicular to the turret, both ends of the partition exceed both ends of the sputtering target; The bottom of the first sputtering target is provided with a magnetic field shielding layer. 10. The device for producing the acetabular cup for artificial joint according to claim 9, characterized in that: the first sputtering target is a graphite target, and the second sputtering target is a titanium target or a tantalum target. 11. The device for producing the above-mentioned artificial joint acetabular cup according to claim 9, characterized in that: the magnetic field shielding layer is a silicon steel gasket. 12. The device for producing the above-mentioned artificial joint acetabular cup according to claim 9, characterized in that: the baffle passes through the turret along the diameter of the turret, and the width of the baffle is larger than that of the turret. The diameter of the stand. 13. The device for producing the acetabular cup for artificial joint according to claim 9, characterized in that the distance between the partition and the circumference of the sputtering target is 2-10 cm. 14. The device for producing the above-mentioned artificial joint acetabular cup according to claim 9 or 13, characterized in that: the sputtering target is rectangular. 15. The device for producing the acetabular cup for artificial joint according to claim 9, 12 or 13, characterized in that: the material of the partition is titanium, aluminum, stainless steel or a combination thereof. 16. The device for producing the above-mentioned artificial joint acetabular cup according to claim 9, further comprising: a second rotating system for driving the turret table to rotate around the central axis of the workpiece holder. 17. The device for producing the above-mentioned artificial joint acetabular cup according to claim 9, characterized in that: the workpiece rack is arranged on the turntable through a bracket rod, and a plurality of workpiece racks are arranged at intervals on the same bracket rod. 18. The device for producing the above-mentioned artificial joint acetabular cup according to claim 9 or 10, characterized in that: the sputtering target is arranged on the inner wall of the vacuum coating chamber. 19. The device for producing the above-mentioned artificial joint acetabular cup according to claim 9 or 10, characterized in that: the arc between the two first sputtering targets is 180 degrees, and the sputtering targets are also Another second sputtering target is included, the two second sputtering targets are arranged oppositely, and the other second sputtering target is in an idle state. 20. A method for producing an artificial joint acetabular cup, using the above-mentioned production device for an artificial joint acetabular cup, for coating a nanometer multilayer film on a substrate to keep the turret rotating at a constant speed, characterized in that it includes: Step 1) Adjust the initial magnetic field strength G1 with the magnetic field shielding layer, so that it meets the requirements of non-destructive sputtering on the surface of the high molecular polyethylene acetabular cup; Step 2) Control the initial working pressure of the coating chamber to be P1, and inject 99.9% argon gas to clean the target and substrate; Step 3) Control the working pressure P2 of the coating chamber, and control the working magnetic field strength of the first sputtering target to G2; the second sputtering target uses the initial I1 current and bias voltage V1 to coat the bottom layer of the pure titanium layer on the substrate for the first predetermined time the sputtering; Step 4) Keep the bias voltage of the second sputtering target constant, and start from the initial current I1, every first interval time T1, the operating current of the second sputtering target is reduced by ΔI1 until its operating current is the first Predetermined current value; at the same time, the first sputtering target starts from the initial operating current I2, the bias value is V2, and every second interval T2, the operating current of the first sputtering target increases by ΔI2 until its operating current is A second predetermined current value; the operating voltages of the first sputtering target and the second sputtering target remain unchanged, and sputtering is performed for a second predetermined duration; Step 5) Keep the operating current of the second sputtering target at the first predetermined current value or set and maintain it at the third predetermined current value, maintain the operating current of the first sputtering target at the second predetermined current value or set the first The operating current of the sputtering target is set and maintained at a fourth predetermined current value, the operating voltages of the first sputtering target and the second sputtering target remain unchanged, and sputtering is performed for a third predetermined time; Step 6) Set the operating current of the second sputtering target to zero, and keep the operating current of the first sputtering target at the operating current of step 3) or set and maintain the operating current of the first sputtering target at the first Five preset current values, performing sputtering for a fourth preset duration. 21. The method for producing an artificial joint acetabular cup according to claim 20, characterized in that: the initial magnetic field strength G1 is 20-30GT; the initial working air pressure is 1.0mPa for P1; the working air pressure P2 is controlled at 130mPa- 250mPa; the working magnetic field strength G2 is 10-150mT; the initial I1 current for the second sputtering target is 3.0-5.0A, the bias voltage V1 is 90-150V, the ΔI1 is 0.5-1.0A, the first predetermined The current value is zero, the initial operating current I2 is 0, the ΔI2 is 0.5-1.0A, the second predetermined current value is 3.0-6.0A, and the bias voltage V2 is 60-100V; the first Both the interval time T1 and the second interval time T2 are positive numbers greater than . 22. The method for producing an acetabular cup for artificial joint according to claim 20, characterized in that: the first predetermined duration is 10-30 minutes. 23. The method for producing an acetabular cup for artificial joint according to claim 20, characterized in that: the second predetermined duration is 10-30 minutes. 24. The method for producing an acetabular cup for artificial joint according to claim 20, characterized in that: the third predetermined duration is 5-10 hours. 25. The method for producing an acetabular cup for artificial joint according to claim 20, characterized in that: the fourth predetermined duration is 10-20 minutes. 26. The method for producing an acetabular cup for artificial joint according to claim 20 or 21, characterized in that: the first interval T1 is 3-10 min; the second interval T2 is 3-10 min. 27. The method for producing an acetabular cup for artificial joint according to claim 20 or 21, characterized in that: the temperature of the whole coating process is controlled at 30-40°C.